Pesticidal derivatives of 0,0-dialkyl-s-thiomorpholinocarbonylmenthyl-thiophosphates and dithiophosphates

ABSTRACT

Phosphates and Thiophosphates containing a special morpholino or isomorpholino residue and having insecticidal, acaricidal and herbicidal properties are disclosed.

United States Patent Beriger llll 3,755,313

[ Aug. 28, 1973 PESTICIDAL DERIVATIVES OF 0,0-DIALKYL-S- THIOMORPHOLINOCARBONYLMENTHYL- THIOPHOSPHATES AND DITHIOPHOSPHATES [75] inventor: Ernst Beriger, Neuallschwil,

Switzerland [73] Assignee: Ciba-Gelgy A.G., Basel, Switzerland [22] Filed: Jan. 17, 1972 211 Appl. No.: 218,552

[30] Foreign Application Priority Data Apr. 16, I968 Switzerland 5552/68 Related US. Application Data [62] Division of Ser. No. 815,522, April 8, l969, Pat.

Primary Examiner Richard J. Gallagher Att0rney Harry Goldsmith et al.

[ 57 ABSTRACT Phosphates and Thiophosphates containing a special morpholino or isomorpholino residue and having insecticidal, acaricidal and herbicidal properties are disclosed.

3 Claims, No Drawings PESTICIDAL DERIVATIVES OF 0,0-DIALKYL-S- THIOMORPHOLINOCARBONYLMENTHYL- THIOPHOSPHATES AND DITHIOPHOSPHATES This is a division of application Ser. No. 815,522, filed on Apr. 8, 1969, now U.S. Pat. No. 3,658,800.

The present invention relates to pesticidal preparations for destroying insects, nematodes and arachnoids (mites, spider mites and ticks) and for controlling grassy weeds and other weeds in important plant cultures, among them also cultures of monocotyledonous plants, in the preemergent and the post-emergent treatment. The new preparations contain, in addition to an active ingredient, one or more of the following additives: a vehicle, a solvent, a diluent, a dispersant, an emulsifier, a thickener, an adhesive, a wetting agent and/or a fertilizer and/or further pesticides.

The active ingredients concerned are compounds of the general formula s mo-iI s-cH-co-Ra in which R. and R each represents an alkyl group having one to four carbon atoms, X represents an oxygen or sulphur atom, R represents one of the following 6- membercd heterocycles containing 2 hereto atoms:

(in which Y represents an oxygen or sulphur atom) and R represents hydrogen or a methyl group.

Some of the active substances are new, and the invention includes these as well.

0,0-dimethyl-S-morpholino-carbamoylmethyldithiophosphate is, for example, a known compound which was observed to have a good insecticidal activity. However, surprisingly the new compounds have a broader activity spectrumagainst animal pests, especially insofar as their systemic activity is concerned. The amount in which they have to be applied for use as insecticides on plants is small; only when greater amounts, such as about 2 kg per hectare, are applied, can the selective herbicidal activity be clearly seen, 'especially in the case of those compounds in which R represents the iso(thio)morpholine residue (a).

On the other hand, the insecticidal, acaricidal and nematocidal activity is equally good with all compounds of the formula 1, independently of the meaning of the substituent R and of whether X represents oxygen or sulphur.

The toxicity towards warm-blooded animals of the compounds is satisfactorily low; thus, the compound No. 11 referred to below has an oral toxicity towards the rat of LD 1 mg per kg bodyweight.

Among animal pests of the classes Hexapoda and Arachnoidea, there may be mentioned, for instance,

the following orders and suborders: Musca, Aphis, Orgyia, Prodenia, Epilachna, Locusta, Rhipicephalus, Dermanyssus, Tetranychus, Aedes, blowfly and all development stages of insects that attack stores, including egg clusters. This enumeration is not complete, but merely emphasizes the most important types of harmful insects and Arachnoidea.

The compounds of the formula 1 can be manufactured by reacting an a-halocarboxylic acid halide or ester in either order with a 1,3- or 1,4-oxazan or 1,3- or 1,4-thiazan and with a dialkyl thiophosphate or dithiophosphate.

In pesticidal preparations and for handling in practice, the new compounds may be in the form of granulates, dusting agents, emulsion concentrates, dispersions or sprays, as for instance for the gas phase application in greenhouses, or as solutions or suspensions in the usual formulation, as described in US. Specification 3,329,702, British Specification 1,047,644 or Swiss Specification 424,359, some examples of which are given below. When using the preparation against animal pests, the use of baits is likewise possible.

The following Examples illustrate the invention, the parts being by weight.

EXAMPLE 1 38.3 Parts of N-chloroacetyl-2,6-dimethyl-1,4 oxazan (b.p. 108C under 0.08 mm Hg; prepared in the usual manner by reaction of chloroacetylchloride with 2,6-dimethyl-1,4-oxazan) were stirred with 39 parts of potassium-dimethyl-dithiophosphate in 260 parts by volume of acetone overnight at room temperature. The reaction mixture was worked up by suctioning off the salts, evaporating the acetone under vacuum and taking up the residue in methylenechloride. The methylenechloride solution was washed with water and then with sodium hydrogencarbonate solution and the solvent was expelled under vacuum at 50C, to leave, as residue, 51 parts of the compound of the formula OH: in the form of a faintly yellowish oil [Compound N0. 1]

The following thiolophophates and dithiophosphates of the formula where manufactured in a similar manner:

Compound No. R R, Y Physical constants 4 CH,- s b.p. 110 0.005

5 C,H,- C H S n 1.5490

The following thiolophosphates and dithiophosphates of the fonnula were manufactured in a similar manner:

The following thiolophosphates and dithiophosphates of the formula X Y I R=0PS II-C0N I on,

were manufactured In a similar manner:

Compound lhysical No. It; X Y R4 constants s 0 1! 3.1204100 s o n 1113 1.5380 s 0 n 71;)152510 s o it my 1.5352 0 o n ru /1.5042 s 0 ll 1113 15226 s s it s s 11 s 0 H 11!) 15205 25 s 0 CH; 1113 15570 0 s o on 7119 15380 22 iso-oiuriso-C H;- s 0 on; 1119 15293 EXAMPLES OF FORMULATION Dusting Agent Equal parts of an active substance of this invention and of precipitated silicic acid were finely ground together. By mixing this powder with kaolin or talcum, a dusting agent preferably containing l to 6 percent of active substance can be manufactured. Spray Powder In order to manufacture a spray powder, for example, the following ingredients are mixed and finely ground together:

50 parts of active substance of this invention 50 parts of Hisil (highly adsorptive silicic acid) 25 parts of bolus alba (kaolin) 3.5 parts of an adduct of p-tertiary octylphenol with ethylene oxide 1.5 parts of sodium l-benzyl-2-stearylbenzimidazole-6,3-disulphonate. Emulsion Concentrate v Readily soluble active substances can also be formulated as emulsion concentrates in the following manner:

20 parts of active substance 70 parts of xylene and 10 parts of a mixture of calcium dodecylbenzenesulphonate and an adduct of an alkyl-phenol with ethylene oxide are mixed. When this mixture is diluted with water to the desired concentration, an emulsion ready for spraying is obtained.

EXAMPLE 2 Compound No. Concentration in ppm b. Activity Against Mites (Dermanyssus Gallinae) Ten to 20 mites per tube were tested as described for the tick test. The value of the concentration of the active substance in the following table represents the minimum content for a percent lethal effect against the mites tested after 3 days:

Compound No. Concentration in ppm EXAMPLE 3 Activity Against Lucilia Sericata (Larvae) A dilution series was prepared with the emulsifiable preparation of an active substance of the formula I. 2 ml of one concentration were mixed in a glass vessel of 10 m1 capacity with 2 g of chopped horse meat, and 20 to 30 freshly hatched larvae were introduced into this vessel. Evaluation was carried out 24 hours later. The indicated concentration in ppm produces a 100 percent lethal effect within 24 hours:

Compound No.

Concentration in ppm EXAMPLE 4 l. Contact Effect Against Musca Domestica (L.)

One half each of a Petri dish was tcated with 1 ml each of an an acetonic solution of compound No. 12, containing 200 and 100 ppm respectively of the active substance. The solvent was then evaporated and deepcooled houseflies introduced into the prepared Petri dishes and the lids were put on. Each dish contained 10' of 3 drops each by mean of a glass rod to the inside of i the lid of the Petri dish. 10 Freshly hatched, unfed flies each were deep-cooled and introduced into the bottom half of a dish. The lid, treated with the preparation to be tested, was then put on. After 4 hours, a 100 percent lethal effect via the intestinal tract was achieved with both concentrations.

EXAMPLE 5 l. Tests with Larvae of Orgyia Gonostigma and Epilachna Varivestis Young Phaseolus plants are immersed in aqueous solutions containing 800 ppm of active substance, allowed to dry and then infested with 5 larvae of Epilachna varivestis in the L-4 stage, whereupon the whole plant is covered with a plastic bag. The same kind of test is carried out with 5 larvae each of Orgyia gonostigma in the L-3 stage and with young mallow plants. The following results were obtained:

Lethal effect at a concentration of Activity Against Aphis Fabae A. The aphicidal effect of the preparation was tested against Aphis fabae (S.) on the test plant Vicia faba, with the use of aqueous emulsions of the active compound No. 11 in concentration series of 800 to I ppm in various ways.

In the contact test, the solution was sprayed all over the infested plant using an atomizer of the type used in chromatography. This test was evaluated 2 days later by counting the killed and the surviving aphids under a handheld magnifying lens. All animals were then removed, and the plants reinfested with a new population. 5 Days after spraying another evaulation was carried out.

B. In order to test the penetration effects, plants were used whose leaves were as far as possible at right angles to the shoot, and the aphids were localised mainly on the underside of the leaves. In this case, spraying was not carried out all over, but vertically from above on to the plants. The penetration test was evaluated 2 days later.

The effect against Aphis fabae is summarised in thefollowing Table, in which the lethal effect is shown in percent:

Concen- Compound No. tration Contact ContactPenetration [ppm] 2 Days 5 Days 2 Days 800 I00 I00 I00 400 I00 80 I00 I I 200 I00 80 I00 I00 I00 0 60 800 I00 I00 100 400 I00 I00 I00 7; I5

200 I00 80 I00 I00 100 0 60 Similar results were obtained with compounds I and 5.

EXAMPLE 7 a. Activity Against Red Spider Mites (Tetranychus Urticae) Dwarf beans in the 2-leaf stage were infested with red spider mites 24 hours before being treated with the active substance, by placing infested pieces of leaves of the grown plants upon the test plants. The treatment of the infested test plants consisted of spraying with the emulsified active substance by means of an atomizer as used in chromatography. 2 Days later, the plants were inspected with binoculars and the number of mites killed was calculated in percent. The effect of compound No. 2 on adults after 7 days in a concentration of 0.08 percent was 100 percent lethal. Similar results were obtained with the other compounds mentioned in Example I.

EXAMPLE 8 In order to test the effect against various pests attacking stores, 5 g each of one of the compounds of the formula I were mixed with g of talcum and very finely ground. In use, this dusting powder produced the following results:

Test Species of Pests Minimum concentration for I00 death in 24 hours exposure time (mg active material per in) Compound No. 2 5 l I German cockroaches (Phyllodromia germanica) I00 I00 50 American cockroaches (Periplaneta americana) I00 I00 200 Russian cockroaches (Blana orienlalis) I00 200 200 Flour beetle imago I00 I00 25 (Tenebrio molilor) Larvae 200 I00 EXAMPLE 9 Test plants Digitaria Panicum Rating 8 9 Plant species unplanted cultivated I ll NNN

l no effect 9 plants destroyed The substances of this invention destroy important grass weeds whereas monocotyledonous cultures, for example, maize or oats and also rice as well as numerous dicotyledonous cultures are not attacked by the substances of this invention.

Quite generally, similar results are obtained with the compounds 15 to 22.

I claim:

1. Compounds of the formula wherein each of R and R represents alkyl of from one to four carbon atoms, R represents hydrogen or methyl, and X represents oxygen or sulfur.

2. The compound of claim 1 in which each of R and R is methyl, R is hydrogen, and X is sulfur.

3. The compound of claim 1 in which each of R and R is ethyl, R is hydrogen, and X is sulfur. 

2. The compound of claim 1 in which each of R1 and R2 is methyl, R4 is hydrogen, and X is sulfur.
 3. The compound of claim 1 in which each of R1 and R2 is ethyl, R4 is hydrogen, and X is sulfur. 